WO1996015182A2 - Perles expansibles a base d'un polymere d'un compose vinylaromatique contenant un agent gonflant ainsi qu'un plastifiant - Google Patents

Perles expansibles a base d'un polymere d'un compose vinylaromatique contenant un agent gonflant ainsi qu'un plastifiant Download PDF

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Publication number
WO1996015182A2
WO1996015182A2 PCT/EP1995/004511 EP9504511W WO9615182A2 WO 1996015182 A2 WO1996015182 A2 WO 1996015182A2 EP 9504511 W EP9504511 W EP 9504511W WO 9615182 A2 WO9615182 A2 WO 9615182A2
Authority
WO
WIPO (PCT)
Prior art keywords
beads
expandable beads
plasticizer
blowing agent
expandable
Prior art date
Application number
PCT/EP1995/004511
Other languages
English (en)
Other versions
WO1996015182A3 (fr
Inventor
Rakesh Jaysinh Paleja
Dominique Paul Vliers
Maria Johanna Willems
Original Assignee
Shell Internationale Research Maatschappij B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Priority to AU41175/96A priority Critical patent/AU4117596A/en
Publication of WO1996015182A2 publication Critical patent/WO1996015182A2/fr
Publication of WO1996015182A3 publication Critical patent/WO1996015182A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene

Definitions

  • the invention relates to expandable beads based on a polymer of a vinylaromatic compound containing a blowing agent and a plasticizer. Moreover, the invention relates to a process for preparing these expandable beads, and articles of expanded beads, obtainable by expanding and fusing these beads.
  • Expandable beads such as for instance the range of expandable polystyrene grades sold by Shell under the trademark "STYROCELL”, find many different uses. Of particular interest are the grades for high strength, low density applications (e.g., the “STYROCELL M” grades) that find use in low density block or continuous board mouldings, large boxes and medium density insulating boards, blocks for veneer cutting, higher strength contour mouldings, packages with wall thickness above 10 mm, fish boxes, floor units, etc.
  • STYROCELL M the grades for high strength, low density applications
  • Expandable beads in the market place are mainly judged by three performance criteria, namely expandability, strength (fusion) and dimensional stability in the form of a short pressure-decay time (i.e., the minimum time the foamed article needs to remain in the mould to avoid warping, etc.). Both high ratings for strength (of the moulded article) and expandability (of the expandable beads) are desired. Moreover, it is preferred that articles of satisfactory strength may be prepared by expanding the expandable beads at low steam pressures, for instance of about 0.6 bar gauge. Finally, the pressure-decay time, which affects the overall cycle time, should be as short as possible.
  • a plasticizer such as for instance white oil and cyclohexane
  • white oil reduces the strength at ordinary steam pressures, whereas at low steam pressures, the strength is hardly improved.
  • the operating window is thus very small.
  • Cyclohexane is a better plasticizer, improving expansion and strength at low steam pressures.
  • cyclohexane is not approved for food contact applications in the European market.
  • US patents Nos. 4,525,484 and 4,459,373 disclose expandable beads based on polystyrene respectively poly- para-methylstyrene having a weight average molecular weight (M w ) in the range of 130,000 to 180,000 that are produced by polymerizing (para-methyl) styrene in aqueous suspension in the presence of blowing agents and of chain transfer agents or (para-methyl) styrene oligomers. These oligomers have a number-average molecular weight (M n ) from 500 to 5,000, preferably 800 to 2,000 and are added at a conversion of from 0 to 90%.
  • M n number-average molecular weight
  • the inventors surprisingly found that, by use of these oligomers in grades of expandable beads based on a polymer of a vinylaromatic compound having a weight average molecular weight (M w ) in the range of 180,000 to 500,000, the afore-mentioned performance criteria could be substantially improved.
  • M w weight average molecular weight
  • the invention provides expandable beads based on a polymer of a vinylaromatic compound having a weight average molecular weight (M w ) in the range of 180,000 to 500,000 containing a blowing agent and a plasticizer in an amount of 0.1 up to 4 %wt (as calculated on the total weight of the beads), wherein the plasticizer is an oligomer of styrene and/or alpha-methylstyrene having a number-average molecular weight (M n ) in the range of 200 to 2,000. (The molecular weights as determined by Gel Permeation Chromatography) .
  • the expandable beads are based on polymers of styrene and/or alpha-methylstyrene, more preferably polystyrene (so-called "EPS").
  • EPS polystyrene
  • the invention may also be applied using expandable beads that are based on copolymers of styrene and a copolymerizable monomer.
  • the more common polymers having an M w in the range of 185,000 to 300,000 are preferred.
  • the plasticizer suitably has an M n in the range of
  • 200 to 1,200 more suitably in the range of 500 to 900.
  • the latter are preferably used in an amount of 1 up to 3 %wt, although more or less may also be used.
  • Blowing agents typically used for preparing the expandable beads comprise volatile (cyclo)hydrocarbons, halogenated hydrocarbons and other volatile organic compounds.
  • pentane is a common blowing agent. It is typically used in an amount of 5.0 to 12 %wt.
  • blowing agent typically used in an amount of 5.0 to 12 %wt.
  • the grade of expandable beads having a low content of blowing agent e.g., containing 3 to 4.9 %wt, is increasing in popularity.
  • the invention also relates to the process for preparing these new expandable beads, by polymerizing the vinylaromatic compound in aqueous suspension in the presence of the plasticizer and adding the blowing agent to the suspension before, during and/or after the polymerization.
  • a radical initiator is used.
  • the polymerization may also be initiated thermally, e.g., when styrene is the (co) onomer. Details with respect to the initiator and other process features are well known in the art.
  • the invention also relates to articles of expanded beads of a polymer of vinylaromatic compounds, obtainable by heating the new expandable beads in a mould at a temperature above the boiling point of the blowing agent and the softening point of the polymer. By heating the new beads, they expand and fuse.
  • These articles have low density (due to the large expandability of the expandable beads) combined with excellent strength, and may be prepared in relatively short production cycles.
  • KRISTALEX 3115, that is a water-clear, highly colour stable, apolar copolymer having an M n of respectively 1200, and that is largely derived from alpha-methylstyrene and styrene monomers, and
  • PICCOLASTIC A5 a viscous liquid mixture of oligomers (trimers and tetramers) of styrene having an M n of 360.
  • GMS glycol dimethacrylate copolymer
  • M w a coating agent whose function it is to prevent agglomeration and static of the expandable beads
  • the plasticizers have been studied in EPS for their expandability-strength balance with respect to regular grade EPS (having an M w of about 175,000) and high strength grade EPS (having an M w of about 200,000).
  • Examples 1 to 4 Comparative examples A to GMS
  • Samples of the EPS grades were prepared by polymerization carried out in a bench-scale (9-litre) reactor.
  • the plasticizer (loading calculated on the sum of styrene monomer and plasticizer) was first mixed with all the styrene at 50 °C for 30 minutes to achieve dissolution. Demineralised water was next poured into the •reactor. Thereafter, polymerization was initiated by radicals of di-benzoyl peroxide (BPO) and t-butyl pe. xybenzoate (tBP) . The concentration of initiators was calculated on the styrene monomer only. Beads of particle size of 0.7-1.2 mm were made using about 0.05 %wt, calculated on the total amount of styrene and plas ⁇ ticizer, of bentonite and gelatine stabiliser.
  • BPO di-benzoyl peroxide
  • tBP t-butyl pe. xybenzoate
  • the blowing agent, pentane, was dosed during the polymerization reaction.
  • the polymerization time for the regular grade EPS was about 210 minutes, whereas the polymerization time for the high strength grade EPS was about 230 minutes, both at 90 to 130 °C.
  • the raw beads so prepared were tumbled in a ribbon blender (a Hermann Linden machine for 1 kg batches, run for 10 minutes) with a coating composition comprising GMS until an uptake of 4 g (0.4 %wt) was achieved.
  • the coated beads were pre-expanded in a batch pre- expander (of the firm Handle) using a steam pressure of 0.20 bar gauge.
  • the pre-expanded beads were allowed to mature overnight in an air-permeable silo and were machine moulded into tiles of 300 mm by 300 mm by 50 mm in a steam-heated enclosed mould operating at 0.6 bar gauge. The pressure- decay time for each tile was noted. Next, the tiles were dried for two days at 70 °C and then conditioned and tested for cross-breaking strength (at break) .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des perles expansibles à base d'un polymère d'un composé vinylaromatique possédant un poids moléculaire moyen (Mw) en poids compris entre 180000 et 500000, et comprenant un agent gonflant ainsi qu'un plastifiant dans une quantité allant de 0,1 à 4 % en poids (du poids total des perles), lequel est un oligomère de styrène et/ou d'alpha-méthylstyrène possédant un poids moléculaire moyen (Mn) en nombre de l'ordre de 200 à 2000. On décrit également un procédé de préparation de ces perles expansibles, ainsi que des articles fabriqués à l'aide de celles-ci et que l'on peut obtenir par expansion puis fusion desdites perles.
PCT/EP1995/004511 1994-11-15 1995-11-15 Perles expansibles a base d'un polymere d'un compose vinylaromatique contenant un agent gonflant ainsi qu'un plastifiant WO1996015182A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU41175/96A AU4117596A (en) 1994-11-15 1995-11-15 Expandable beads based on a polymer of a vinylaromatic compound containing blowing agent and plasticizer

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP94203333 1994-11-15
EP94203333.3 1994-11-15
EP94203332 1994-11-15
EP94203332.5 1994-11-15

Publications (2)

Publication Number Publication Date
WO1996015182A2 true WO1996015182A2 (fr) 1996-05-23
WO1996015182A3 WO1996015182A3 (fr) 1996-08-01

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/004511 WO1996015182A2 (fr) 1994-11-15 1995-11-15 Perles expansibles a base d'un polymere d'un compose vinylaromatique contenant un agent gonflant ainsi qu'un plastifiant

Country Status (2)

Country Link
AU (1) AU4117596A (fr)
WO (1) WO1996015182A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2858977A1 (fr) * 2003-08-21 2005-02-25 Bp Chem Int Ltd Composition de polystyrene expansible, procede de fabrication d'objets en polystyrene expanse de moyenne densite, et perles pre-expansees en polystyrene de moyenne densite

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE633239A (fr) * 1963-05-28
US4520135A (en) * 1982-07-01 1985-05-28 Basf Aktiengesellschaft Particulate polystyrene containing blowing agent and having improved expandability
EP0217516B1 (fr) * 1985-08-16 1991-09-04 The Dow Chemical Company Particules expansibles à base de polymères vinyl(idène)aromatiques, leur procédé de préparation et articles formés à partir de ceux-ci

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE633239A (fr) * 1963-05-28
US4520135A (en) * 1982-07-01 1985-05-28 Basf Aktiengesellschaft Particulate polystyrene containing blowing agent and having improved expandability
EP0217516B1 (fr) * 1985-08-16 1991-09-04 The Dow Chemical Company Particules expansibles à base de polymères vinyl(idène)aromatiques, leur procédé de préparation et articles formés à partir de ceux-ci

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2858977A1 (fr) * 2003-08-21 2005-02-25 Bp Chem Int Ltd Composition de polystyrene expansible, procede de fabrication d'objets en polystyrene expanse de moyenne densite, et perles pre-expansees en polystyrene de moyenne densite
WO2005019319A1 (fr) * 2003-08-21 2005-03-03 Innovene Europe Limited Composition de polystyrene expansible
US8536240B2 (en) 2003-08-21 2013-09-17 Ineos Commercial Services Uk Limited Expandable polystyrene composition

Also Published As

Publication number Publication date
WO1996015182A3 (fr) 1996-08-01
AU4117596A (en) 1996-06-06

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